Detergent composition containing monoamide hydrocarbyl sulfonic acid salts of hydrocarbyl succinic acid

ABSTRACT

DETERGENT COMPOSITION CONTAINING AS ACTIVE MATERIALS MONOAMIDE HYDROCARBYL SULFONIC ACID SATS OF HYDROCABYL SUCCINIC ACID OF THE FORMULA   X-OOC-CH(-R1)-CH2-CO-N(-R3)-R2-SO3-Y OR   X-OOC-CH2-CH(-R1)-CO-N(-R3)-R2-SO3-Y   IN WHICH E1 IS A HYDROCARBYL GROUP OF 8 TO 30 CARBON ATOMS; R2 IS A HYDROCARBYLENE GROUP OF 1 TO 8 CARBON ATOMS; R3 IS H, A HYDROCARBYL GROUP OF 1 TO 8 CARBON ATOMS, OR -R2-SO3Y; X IS H OR Y; AND Y IS A WATERSLUBLE SALT-FORMING CATION; AND NON-PHOSPHATE BUILDERS AND ADDITIVES.

United States Patent U.S. Cl. 252-526 3 Claims ABSTRACT OF THE DISCLOSURE Detergent composition containing as active materials monoamide hydrocarbyl sulfonic acid salts of hydrocarbyl succinic acid of the formula in which R is a hydrocarbyl group of 8 to 30 carbon atoms; R is a hydrocarbylene group of 1 to 8 carbon atoms; R is H, a hydrocarbyl group of 1 to 8 carbon atoms, or -R --SO Y; X is H or Y; and Y is a watersoluble salt-forming cation; and non-phosphate builders and additives.

CROSS-REFERENCE TO RELATED APPLICATION This application is a division of US. application Ser. No. 885,977, filed Dec. 17, 1969, now Pat. No. 3,732,290.

BACKGROUND OF THE INVENTION The present invention is concerned with the field of synthetic detergents, and more particularly with monoamide hydrocarbyl sulfonic acid salts of hydrocarbyl succinic acid suitable for use as active detergent components in biodegradable and phosphate-free detergent compositions.

Increased concern over Water pollution has resulted in significant changes in household detergents. Initially the major, emphasis was placed upon producing biodegradable surface active components for detergent compositions. The resulting shift from surface activematerials containing branched hydrocarbyl groups to linear materials such as linear alkyl benzene sulfonates and alpha olefin sulfonates has resulted in a significant decrease in pollution attributed to non-biodegradability. Thus, the undesirable foam which had formerly been carried by sewage effluents into the lakes and streams is no longer increasing because the linear alkyl groups are susceptible to bacterial attack. However, the shift to the linear materials has placed an enormous burden upon the chemical industry in attempting to meet the ever increasing demand for the linear detergent precursors.

. The previously mentioned conventional detergents, the branched and linear alkyl benzene sulfonates and the alpha olefin sulfonates are inadequate inordinary detergent uses in respect to soil removal in the absence of sequestering type builders such as phosphates. Increasing evidence appears to "indicate that phosphates contribute to the growth of algae in the Nations streams and lakes. This algae growth poses a serious pollution threat to the maintenance of clear good domestic water supply. Thus,

it is important that detergent compositions be provided 3,793,226 Patented Feb. 19, 1974 SUMMARY OF THE INVENTION- Novel compositions of matter useful as phosphate-free detergent compositions comprise monoamide hydrocarbyl sulfonic acid salts of hydrocarbyl succinic acid. These materials may be represented by the following structural formula: i I

inwhichu, v,xandy areOor l,thesumof uandvis1, the sum of x and y is l, the sum of u and x is l, the sum of v and y is 1, R is a hydrocarbyl group of 8 to 30 carbon atoms; R is a hydrocarbylene group of 1 to 8 carbon atoms; R is H, a hydrocarbyl group of 1 to 8 carbon atoms, or R S0 Y; X is H or Y; and Y is a water-soluble, salt-forming cation. In a preferred embodiment, the hydrocarbyl radical, R contains from 12 to 22 carbon atoms. It is also preferred that X and R; are H and R is ethylene.

The salt forming cations represented by Y in the above formula are exemplified by alkali metal and alkaline earth metal cations, ammonia, and various organic cations such as tertiary amino materials. Examples of these cations are those of the following structure:

Generally the alkali metal cations are preferred, and most particularly sodium ion is preferred. a f

In general, when the compounds of the present-invention are formulated as detergent compositions, additional compatible ingredients may be incorporated therein to enhance their detergent properties. Such ingredients may include, but are not limited 'to, anti-corrosion, anti-redeposition, bleaching, and sequestering agents, and cer tain organic and inorganic alkali, alkaline earth salts other than'phosphates, such as inorganic sulfates, carbonates or borates and organic salts of polycarboxylic acids, e.g., trisodium salt of nitrilo triacetic acid,- the tetrasodium salt of ethylene diamine .tetracetic acid, the polysodiurn salt of ethylene-maleic acid'copolymer, etc.

Surprisingly, the novel compounds of the present invention exhibit high detersive characteristics in the absence of phosphate builders. In particular, formulations containing sodium or potassium sulfates as a major-additive ingredient are preferred. As previously noted,-this-is significant in view of the fact that most household heavyduty detergent compositions require the presence of sequestering-type builders such as phosphates in order-to achieve satisfactory detergency.

In general, compatible ingredients other than-water may be employed in amounts ranging from 60 to 900 parts and, preferably, from 70 to 250 parts by weight per parts of the active material. In addition, the detergent compositions may comprise from 0 to 700 parts by weight of water per 100 parts of active material. The lower range of water concentration is used for compounding particulate formulations which may contain up to about 15 parts of water per 100 parts of the active material. The

upper range of water concentration is used to prepare 2 liquid formulations. For this use a range of 100 to 400 parts of water per 100 parts of the amide is preferred.

The compounds of this invention are preferably prepared by the direct reaction of a hydrocarbyl succinic anhydride with the aminohydrocarbyl sulfonic acid salt. The succinic anhydride compounds are well known in the art and are produced by the condensation of maleic anhydride with a mono olefin. This reaction which leaves residual unsaturation in the adjunctive hydrocarbyl group yields materials which may be characterized as alkenyl or substituted alkenyl succinic anhydrides. Mild hydrogenation of these materials may be eflected to produce alkyl or substituted alkyl succinic anhydrides which are of equal effectiveness in producing the active compositions of this invention. Examples of the hydrocarbyl radicals include alkyl or alkenyl of aromatic substituted alkyl or alkenyl materials. 'Examples of the alkyl groups include tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, etc. The alkenyl groups include dodecenyl, tridecenyl, tetradecenyl, 'pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl and tricontenyl, etc. These groups may be either straight or branched chained. The point of attachment may be at any place on the chain. Aromatic substitution may be employed if appropriately placed.

The amidification reaction is accomplished by contacting stoichiometric quantities of the anhydride with the amino sulfonic acid salts at temperatures in the range of 100 to 220 C. These salts, such as the taurine salts, are readily available in commercial quantities. Temperatures higher than about 250 C. should be avoided because significant quantities of succinimides which are not suitable for the purpose of this invention may be produced.

The amino hydrocarbyl sulfonic acids which are employed in the amidification reaction are of the formula:

IiIH-RQ-SOaY Rs in which R R and Y are as previously described. Thus R may be saturated or unsaturated, aliphatic, alicyclic or aromatic and the groups -S Y and -NH-R may be attached at any point on the hydrocanbylene radical. Examples of the materials include salts of taurine, N- methyltaurine, N-ethyltaurine, N-hexyltaurine, amino aromatic sulfonates such as ortho, meta and para amino benzene sulfonic acids, 4-amino-2-toluene sulfonic acid, 4-amino-2-xylene sulfonic acid, etc.

The following examples describe the preparation of the detergent compounds of this invention. The examples are intended to be illustrative and non-limiting.

Example l- Preparation of hexadecenyl succinic anhydride A mixture of 336 g. (1.5 mols) of an alpha olefin having an average of 16 carbon atoms and an average molecular weight of 224 was stirred slowly with 49 g. (0.5 mols) of maleic anhydride in a 1-liter, 3-neck round bottom flask equipped with an explosion-proof stirrer, a drying tube condenser, and dropping funnel, and continuously flushed with nitrogen. The reaction was continued for about seven hours at a gradually increasing temperature starting at 85 C. and stopping at 238 C. At the end of this time, infrared analysis showed less than 1% of maleic anhydride remaining. The mixture was transferred to a distillation flask. Excess olefins were removed by distillation at approximately 1 mm. pressure until about 5% olefin remained. The stirred bottoms product from this distillation was then heated and filtered through Celite to give g. of crude alkenyl succinic anhydride.

Example 2--Hydrogenation of C alkenyl succinic anhydrides to produce alkyl succinic anhydride In a 500 ml. Fisher-Porter bottle, 40.0 g. of 2-nhexadecenyl succinic anhydride was dissolved in 250 ml. of absolute ethanol. To this was added 4.0 g. of palladium on carbon catalyst. Hydrogen was added to the bottle to give 60 p.s.i.g. of pressure. The contents were heated to 50 C. and agitated with incremental addition of hydrogen until a total of 200 p.s.i. of hydrogen was taken up. The solution was filtered while warm to remove the catalyst, and then the alcohol was removed by evaporation at 50 C. to give 37 g. of hexadecyl succinic anhydride. An infrared spectrum showed the complete absence of double bonds.

Example 3.--Preparation of monoamide of C alkyl succinic anhydride with taurine 12.5 g. (0.1 mol) of taurine was dissolved in 100 ml. of water in a beaker. Sodium hydroxide was added to a pH of 9-10. The material was then dried by evaporation. 2.94 g. (.02 mol) of the dry salt was combined with 6.44 g. (.02 mol) of alkyl succinic anhydride produced in Example 2. The mixture was placed in a beaker and heated to its melting point and stirred for two hours. The material was allowed to cool, was dissolved in ethanol and recrystallized. Based on a hyamine titration, the recovered product was 97% pure. The product had infrared spectra which showed strong amide adsorptions at 1690l710 cm.- and sulfonate absorptions at 1170- 1230 and 1050 cmr indicating the production of the monoamide sulfonate salt of the anhydride. The presence of hydrogen ion indicates that the carboxylic group remains unneutralized.

Example 4.Preparation of monoamide of C alkyl succinic anhydride with -aminophenyl sulfonic acid The same procedure was followed as in Example 3, using 9.66 g. C alkyl succinic anhydride (0.03 mol) and 5.85 g. (.03 mol) of the sodium salt of ;;-aminophenylsulfonic acid.

Detergency of the compounds of the present invention is measured by their ability to remove natural sebum soil from cotton cloth. By this method, small swatches of cloth, soiled by rubbing over face and neck, are washed with test solutions of detergents in a miniature laboratory washer, and the reflections of the various cloths measured and compared. The results obtained are expressed as relative detergency values. The relative detergency value is obtained by comparmg and correlating the reflectance value results from the test solution with the results from two defined standard solutions.

The two standard solutions are selected to represent a detergent system exhibiting relatively high detersive characteristics and a system exhibiting relatively low detersive characteristics.

By testing each soiled cotton cloth against the standardized solutions, as well as the test solutions, the results can be accurately correlated. The two standard solutions were prepared from the following detergent formulations:

Low detersive standard (Control A) Ingredient:

By the method of House and Darra h A lstry, 26 1492 1954). g nalyflcal Chem High detersive standard (Control B) 6 formulations could be used to wash different parts of the same swatch. This arrangement ensured that all four fori i welght m mulations were working on identical soil (natural facial Linear alkylbenzene sulfonate (LAS) 7.5

5011). Relative detergency (RD) values were calculated Tallow alcohol Sulfate 10 from soil removal (SR) accordin to th e uation' Sodium triphosphate 47-5 S g 6 q Water Sodium RD=2+4. P rce ruw cen ControlA Sodium silicate 5 Percent Control B Percent Conti-ol A carbcxymethykenulme f 1 1 For comparison, a commercial available active The standard exhibiting high-detersive characteristlcs was LAS detergent formulation was measured at 0.1 percent prepared by dissolving a relatively large amount of the by weight concentration in 50 p.p.m. hard water. above formulation (2.0 g.) in 1 liter of 300 p.p.m. hard Detergency test results obtained on a variety of the water (calculated at A calcium carbonate and mag- 7 subject monoamide phosphate-free formulations are given nesium carbonate). The low detersive standard contained in the following table. The components of each amide a relatively low concentration of the formulation (1.0 g.) are identified by reference to the structural formula in dissolved in 1 liter of 300 p.p.m. water (same basis). column 2 of the specification. In each test Y is Na.

TABLE Active B m i Amide components m er ggiii e riii imii Weight Weight X percent Type percent 0.1% 0.2%

Phosphate.- 6.2 6.6 15 NTiu 20 5.7 6.4 25 o 3.9 4.6 15 20 5.4 6.7 25 o 4.1 5.0 15 20 as 5.5 25 o 3.0 4.1 15 20 3.4 6.4 o 15 no a7 6.0 10. 25 o 5.3 6.0 11-. 15 20 4.9 6.4 12-. 25 0 a6 5.3 13.. 15 20 4.5 5.6 14.. 15 20 4.9 6.3 15 25 0 as 5.7 15 20 4.9 6.1 25 0 3.6 as 15 20 4.0 6.0 25 0 4.2 5.2 15 20 5.5 5.4 o 2.2 3.2 0 4.6 5.5 20 4.5 6.4

1 Linear alkyl groups derived from l-olefins, except linear alkenyl groups in tests 8, 14-15. See footnote 7. 1 Percent concentration by weight of detergent formulation in water of p.p.m. hardness.

8 Commercial hnear alkyl benzenesnlrouate composition containing about 20% LAS.

4 Monoarmdes oi hydrocarbyl snccrmc acids with amino hydrocarbyl sulionic acid salts.

5 Tnsodium mtnlotrlacetic acid. Hydrolyzed ethylene-maleic anhydrlde eopolymer (sodium salt). 1 C linear alkenyl group derived from l-eicosene.

The test solutions consisted of monoamides of hydrocarbyl snccinic acids prepared in accordance with Example 2 and formulated with trisodium nitrol triacetic acid and other ingredients to give the following phosphatefree formulation:

Ingredient: Weight percent Monoamide detergent active l5 Trisodium nitrilo triacetic acid 20 Sodium sulfate 49 Carboxymethylcellulose 1 Sodium silicate 7 Water 8 Ingredient: Weight percent Monoarnide detergent active 25 Sodium sulfate 59 Carboxymethylcellulose 1 Sodium silicate 7 Water 8 The miniature laboratory washer used was so constructed that the two standard formulations and two test The results set forth in the above table show the eifectiveness of the amide detergents of this invention in the absence of any builder and particularly in the presence of nonphosphate builders. Thus the tests illustrate that effective detergent compositions can be provided in the absence of the undesirable phosphate builders. It may be noted from a comparison of the results of tests 22 and 23 with tests 4 and 5 that detergent activity is present when the free carboxyl group is either in the acid or salt form; however, the acid form is preferred.

As will be evident to those skilled in the art, various modifications of the present invention can be made or followed in light of the foregoing disclosure and discussion without departing from the spirit or scope of the following claims.

I claim:

1. A phosphate-free detergent composition consisting essentially of:

(1) as an active ingredient, the compounds of the formula in which u, v, x and y are 0 or 1, the sum of u and v is 1, the sum of x and y is 1, the sum of u and x is 1, the sum of v and y is 1, R is an alkyl or alkenyl, or aromatic-substituted alkyl or alkenyl group of 8 to 30 carbon atoms; R; is an aliphatic, alicyclic or .7 8 aromatic hydrocarbon group of 1 to 8 carbon atoms, References Cited R is an aliphatic hydrocarbon group of 1 to 8 car- UN STATES PA TS I bon atoms; X is H 01' Y; and iS an metal, 2 0 9 34 937 Doser et 1 alkaline earth metal, or a tertiary lower hydroxy 2,192,90 3 1940 nf et 1, 2 0 45 alkyl amino cation; and l 5 2,368,067 1/ 1945 Lynch 260-481 R (2) water soluble inorganic builder salts and organic Y -t-i-- g aeger e a l olyelectrolytes in an amount of from 60 to 900 3,317,589 Vitalis et all 7 260;.513 N parts by weight per 100 parts of active ingredient. H 2. A detergent composition as in claim 1 wherein in 10 MAYER WEINBLA'IT, Primary Examiner the active ingredient X is P. WILLIS, Assistant Examiner 3. The detergent composition of claim 1 1n which the a Water soluble inorganic builder salt is an alkali metal U.S. Cl. X.R. v or alkaline earthv metal sulfate, borate, or carbonate. 15 252-121, 526, 535, 538, 545, 557; 26 045 8, 507, 513 

